TWI375347B - Manufacture method of bi-polar plates of fuel cell and bi-polar plates thereof - Google Patents

Manufacture method of bi-polar plates of fuel cell and bi-polar plates thereof Download PDF

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Publication number
TWI375347B
TWI375347B TW098139650A TW98139650A TWI375347B TW I375347 B TWI375347 B TW I375347B TW 098139650 A TW098139650 A TW 098139650A TW 98139650 A TW98139650 A TW 98139650A TW I375347 B TWI375347 B TW I375347B
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Taiwan
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fuel cell
bipolar plate
graphite film
powder
graphite
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TW098139650A
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Chinese (zh)
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TW201119119A (en
Inventor
Wen Lin Wang
Chun Hsing Wu
Kan Lin Hsueh
Huan Ruei Shiu
Wen Chen Chang
Fang Hei Tsau
Lung Yu Sung
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Ind Tech Res Inst
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Priority to TW098139650A priority Critical patent/TWI375347B/en
Priority to US12/708,192 priority patent/US8546046B2/en
Publication of TW201119119A publication Critical patent/TW201119119A/en
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Publication of TWI375347B publication Critical patent/TWI375347B/en
Priority to US14/015,968 priority patent/US8841045B2/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023Porous and characterised by the material
    • H01M8/0241Composites
    • H01M8/0245Composites in the form of layered or coated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/18Layered products comprising a layer of metal comprising iron or steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0206Metals or alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/02Details
    • H01M8/0202Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0204Non-porous and characterised by the material
    • H01M8/0223Composites
    • H01M8/0228Composites in the form of layered or coated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/18Fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/10Methods of surface bonding and/or assembly therefor

Abstract

A method for fabricating a bi-polar plate of a fuel cell and the bi-polar plate thereof are presented. A graphite film is formed first. Next, a polymeric material added with electrically conductive powder is coated on a surface of a metal substrate. The graphite film is disposed on the polymeric material and the polymeric material is hardened to form an adhesive layer, such that the graphite film is attached on the surface of the metal substrate.

Description

1375347 六、發明說明: 【發明所屬之技術領域】 本發明係有關於一種燃料電池,特別θ — 板的製備方法及其雙極板。 種燃料電池之雙極 【先前技術】 燃料電池_ _由於具有高效率反應 等特性,因此已廣泛的應用於電力、巧、=作讀及低㈣ 菜運輪、太空、軍辜茸 各領域中。燃料電池係-種可將化學能連 早争寻 不斷直接轉變為電能 之發電裝置,燃料電池工作時,燃料氣體(如 备#、、 風氮)與助燃劑(如 氧亂)W輸送麵料電池的陽極與陰極,藉 將化學能轉變為電能。 4原反應 習用的燃料電池單體結構大致是由—陽極板、—陰極板,及 认-片關電解質膜所構成,稱為單電池。然而,:實際使用 時,是需要將多個單電池相互串聯,以取得較大的輸出電壓,相 鄰的燃料電池單體係共用同—電極板,係分別做為兩相鄰燃料電 池早體的陽極嫌極,恤—雜缺_細聊_此)。 又極板的材質主要為石墨材料、複合碳材及金屬材料等具有 问導電度的材料’為了因應市場上對於燃料電池必須兼具高電力 密度與輕量可搞的需求,勢必得將雙極板㈣化。$,要將石墨 2或複合碳板的厚度控制的極薄,將造成雙極板的氣密性不佳及 結構強度不足關題,或是受限於石墨硬度低及延展性不佳等材 料特性’導致加卫或使肖時容$碎^。 } 1375347 金屬材質加工容易,適合大量生產,且電傳導度與熱傳導度 亦相當優異’因此若是選用金屬#料可製成厚度較薄且質量較輕 的雙極板。但是,在燃料電池工作過程中,燃料或氧化劑發生反 應後容易造成金屬雙極板表面的氧化及腐姓現象,導致燃料電池 的性能下降,使用壽命減短等問題。若是選用耐腐蝕之貴金屬(例 如金(Au)或鉑(Pt))製作雙極板,或是在金屬雙極板表面鍍上一層貴 金屬材質的保護層’其製造成本又太高。 以不鏽鋼材料(stainless steel)、銘材料(A1)、或鈦材料(Ή)等抗 腐钱金屬材m的雙.極㈣f,錢極板表面雖可形成由氧化 物組成的緻密氧化層,謂止電解質造成雙極絲面的腐钱作 用’但這些氧化層卻也導致表面接觸阻抗的增加,使得雙極板傳 導電子的能力將低,因畴致燃料f池的總輸出賴亦隨之下降。 美國專利f 6錢_鮮糧㈣τ簡稱_案)揭露一種燃 料電池的雙極板、轉,料_紐上讀駄式細降咖㈣ 披覆同为子材料’並經由高溫裂解㈣咖叫反應而與基板相結 合’而此-高分子材料中添加有至少、9〇%的導電石墨,藉以隔絕 外界環境對不細基板產生腐倾氧化作用,肖時具備導電特性。 但,由於040案係透過倾方式形成導電保護膜,而其高分 子材料㈣频於高溫轉過程中揮發,使得最後成型的導電保 伽内產生非衫的小氣孔,因而導致保護膜的緻密性不佳,而 乂些小氣孔即成為燃料電池的酸性溶液滲入雙極板内的通道。因 匕〇4〇本必須在不鏽鋼基板的表面上塗覆多層高分子材料,並經 1375347 過多道高溫裂解工序,方可避免上述問題的產生,但卻使得雙極 板的加工程序過於複雜,且製造成本亦過於昂貴。 【發明内容】 鑒於以上的問題,本發明提供一種燃料電池之雙極板的製備 方法及燃料電池之雙極板,藉以改良習用燃料電池之雙極板因石 墨材料的特性而導致使社多所受限,並錢用效能不佳,以及 金屬材料製成的雙極板後續必須經過多道表面處理程序,而造成 加工程序複雜及製造成本過高等問題。 〃本發明所揭露之燃料電池之雙極板的製備方法,其步驟首先 係提供一金屬基板’並且成型一石墨膜。接著提供-高分子材料 至金屬基板的表面上,且高分子材料内添加有導電粉末。將石翼 膜設置於高分子·上,並硬化高分子材仙__著層,ς 石墨膜結合於金屬基板上。 本發明之爾幅之雙極板包括有—金屬基板、_黏著層、 及-石墨臈’其中黏著層係設置於金屬基板的—表面上^ ‘層内具有導電粉末,石墨膜係設置於黏著層上。· 且^ 本剌絲完成石類㈣備工序,接著縣 將 墨膜與金屬基板相互結合,並非預先混合石墨與高分ζ:將石 將此-混合材料成型於金屬基板上,本發明之 曰,再 與習用雙極板的製傷步驟不同。 又反的製備方法 因此,本發明的製備方法可避免石墨膜 時,其内部產生大量的缺陷(d _:料層)在成型 鳍从向雙極板的使用效能 5 1375347 及使用壽命,以達到輕薄化、可大量生產、抗腐蝕性能良好、及 降低製造成本等功效。 以上之關於本發明内容之說明及以下之實施方式之說明係用 以示範與轉本發明H並且提供本發明之專利冑請範圍更 進一步之解釋。. 【實施方式】. 「第1圖」及「第2圖」至「第6圖」所示為本發明一實施 例之步驟流程圖與分解步驟示意圖。 如「第2圖」至「第3D圖」所示,並配合「第丨圖」之步驟 流私5兒明一併參酌,本發明之燃料電池之雙極板的製備方法,首 先係提供一金屬基板210(步驟1〇〇),此;一金屬基板21〇的材質可 為銘材料(A1)、鈦材料(Ti)、鎳材料,銅材料((::11)、.鉻材料((:1>)、 錫材料(Sn)及其合金、或是不鏽鋼材料steei) _,而本實施 例之金屬基板210係選用316L不鏽鋼材料,其厚度為01毫米(_) 至0.2毫米(_)之間’但並不以本實施例為限。另外,本發明所 揭露之燃料電池為薄膜燃料電池(proton exchange membrane cell ’ I^MFC),但並不,以此為限。 , 八接著,成型一石墨膜220(步驟110),而此一石墨膜22〇係藉 由一治具300壓合成型。詳細而言,石墨膜22〇的成型製程係先 :供一治具300 ’接著將定量的石墨材料4〇〇,例如天然石墨或是 人造石墨(或稱膨脹石墨)填充至治暑300中,再對治具3〇〇施以一 壓合力量,以密壓成型出高純度且緻密的石墨膜22〇。本實施例之 6 1375347 石墨膜2 220 _合成型力量至少為80公斤力/每平方公分 (kgW) ’若是壓合力量低於8G公斤力/每平方公分時,石墨材料 將無法形成如本實施例之絲平整_層,並且其石墨膜的緻密 腐钱效果亦相對變差。本實施例之石墨膜挪的微結構請 參閱「第7圖」所示的掃描式電子顯微鏡(s_mg electr〇n nncroscopy,SEM)示意圖。 本實施_石墨膜細厚度為GG1絲(麵)至丨毫米㈣ 之間’細熟悉此概術者,可藉由輕^錢添加量或是壓合 力道,以對應改變石伽220的厚度與緻密度,並不以本實施例 域。另外,亦可於石墨膜22G加|成獅過程中,額外施加一 熱量至治具3GG,以增加石麵22G的結合性與緻密度。 如「第3D圖」所示,並配合「第1圖」之步驟流程說明一併 參酌’本發明之簡電池之雙極㈣製備方法更包括有形成一流 道221於石墨膜220的一側面上(步驟m)。值得注意的是,石墨 膜220上的流道221可於石墨膜22〇 M合製備過程中即同時形成 於石墨膜22G的-侧面上,或者是於雙極板的後續製程中另行形 成於石墨膜22G上’、其流道221的成形步驟並不限定於本發明所 揭露的實施例所載。 請繼續參閱「第4A圖」至「第4C圖」所示,並—併參酌「第 1圖」的步驟流程圖。接著’提供一高分子材料23〇,例如為熱硬 化树知材料'光硬化樹脂材料、或是化學硬化樹脂材料、添加導 電粉末231至高分子材料230内,而導電粉末231的添加範圍為} 7 個重量百分比(lwt%)[2〇個重量百分比(lwt%)之間,且導電粉 了為金(Au)、始(Pt)、纪(ρφ、鈇(Ti)、鎮(Ni)、鉻(Q·)或其 合金等金屬粉末、石墨粉末、碳粉末、奈米碳管、碳纖維、或是 ^混合粉末’其導電粉末231的粒徑尺寸控制在i奈米㈣至2〇〇 不米(nm)之間。然而’熟悉此項技術者,可根據實際使用需求而 選用’、良好電特性的粉末種類,以及適合的粉末粒徑尺寸,並 不以本發明所揭露之實施例為限。 以機械設備或是人工方式對添加有導電粉末231的高分子材馨 料230進行授拌,使導電粉末231均勻的散佈於高分子材料⑽ 内’:接著將含有導電粉末现的高分子材料23〇塗覆於金屬基板’ ho的一表面上(步驟120) ’而本實施例之高分子材料23〇可透過 到刀塗佈、旋轉塗佈、噴射塗佈、狹縫塗佈、或滾壓塗佈等方式 均勻塗覆於金屬基板_21〇上。 如「·第1圖」及「第.5圖」、「第6圖」所示,將製備完成的 石墨碎22〇設置於高分子材料MO上(步驟),並且石墨膜22〇 φ 係以具有流道221的另一側面貼覆於高分子材料bo上。接著, 硬化高分子材料230以成型為黏著層232(步驟14〇),使得石墨膜 220得以穩固的結合於金屬基板21〇上,以成為燃料電池之雙極板 200結構。其中:,本實施例之黏著層232的厚度係控制在1〇微米(啤) 至600微米(μιη)之間’但並不以此為限。 睛參閱「第8Α圖」及「第犯圖」所示之極化曲線分析圖,. 其抗腐蝕試驗所使用的腐蝕液為〇·5莫耳濃度_的硫酸溶液,測 Ϊ375347 • 試時間為1000小時。 「第8A圖」所示為未披覆有本發明之石墨膜的316L不鏽鋼 基板進行抗腐蝕試驗的動態極化曲線,實線線段為316L不鏽鋼基 板未浸泡於硫酸溶液時的極化曲線’虛線線段為316L不鏽鋼基板 浸泡於硫酸溶液内1000小時後的極化曲線。由圖中可得知,當未 披覆有石墨膜之316L不鏽鋼基板浸泡於硫酸溶液内丨〇⑻小時 後,其腐蝕電流密度值由未浸泡於硫酸溶液時的約1〇·7安培/每平 • 方公分(Amps/cm2)增加至約10·6安培/每平方公分(Amps/cm2),顯 見未披覆有石墨膜之316L不鏽鋼基板長時間處在腐钱環境中,其 抗腐蝕特性嚴重衰退,進而影響燃料電池之雙極板的可靠度。 「第8B圖」所示為披覆有本發明之石墨膜的316乙不鏽鋼基 板進行抗腐蝕試驗的動態極化曲線,實線線段為316L不鏽鋼基板 未浸泡於硫酸溶液時的極化曲線,虛線線段為316L不鏽鋼基板浸 泡於硫酸溶液内1000小時後的極化曲線。由圖中可得知,當披覆 鲁有石墨膜之不鐘鋼基板浸泡於硫酸溶液内..小時後.,.其 .腐㈣流密度贿未浸泡於雜溶液_触電流纽值接近, 並無明顯的變化,顯見披覆有本發明之石墨膜的316L不鐵鋼基板 長時間處在腐鱗境中,仍然維持良好的抗腐钱特性。 請參閱「第9A圖」及「第9B圖」所示之應力_界面接觸阻抗 的曲線刀析® ’X軸為應力值,其單位為牛頓/每平方公分⑽^2), Y轴為電阻係數(I.C.R.),其單位為毫歐姆父每平方公分㈣⑽巧。 其中’.♦们虎之線段為未披覆有;5墨膜之316L不鏽鋼基板力 1375347 _界面接觸阻抗曲線;匾:符號的曲線線段為坡覆有石墨膜,且黏著 層内含有導電粉末之316L不鏽鋼基板的應力、界面接觸阻抗曲 線;▲符號的曲線線段為坡覆有石墨膜,且黏著層内未含有導電 粉末之316L不鏽鋼基板的應办-界面接觸阻抗曲線。 由「第9A圖」中可清楚得知,披覆有石墨膜但黏著層内未含 有導電粉末的3说確鋼基板,其界面接觸阻抗值明顯高於其他 兩組不鏽鋼基板’顯見本發明之黏著層添加有導電粉末確實可以 有效降低雙極板的界面接觸阻抗’本發明之雙極板由石墨膜提供 水平面的導電性能,轉著層内的導餘末提供垂直面的導電性_ 能,使得本發明之雙極板具備相當良好的導電特性。 另外’請參閱「第9B圖」,並且比較未披覆有石墨膜之316乙 不鏽鋼基贿披覆有石墨膜且黏著層内含有導電粉末之3亂不 義基板的應力界面接觸阻抗曲線,其未披覆有石墨膜之31化 不.鏽鋼基板需要施加-定程度的應力方可降低其界面接觸阻抗 值,而坡羣有石墨膜且黎著層内含有導電粉末之316L不鏽鋼基板 之界面接觸阻抗值則不受應力值的影響而產生大幅度的變化。· 本發明所揭露燃料電池之雙極板的製備方法,其係先完成石 墨膜的氣爾工序’再藉由硬化高分子材辨所形成的黏著層以將石 墨膜與金屬棊板相互結合,因此本發明之雙極板的製備方法與習 用雙極板的製備步驟不同,有效改善f用雙極板之導電保護層於 乾燥成膜時造成大量缺陷生成的問題,並且本發明之製備方法可 廣泛的應用於高溫或低溫燃料電池之雙極板的製造。 10 1375347 本剌_石_與⑽相雙重_,叫錄隔金屬基 燃m叙魏錄制,如提高紐㈣導電效 :、使用詩、及可靠度’並且達到降低製造成本、抗細生能 良好、及可大量生產等功效。 雖然本發明之實施例揭露如上所述,然並非用以限定本發 明,任何熟習相關技藝者,在不脫離本發明之精神和範圍内,舉 凡依本發”請範騎述之職、構造、概及精神當可做些許1375347 VI. Description of the Invention: [Technical Field] The present invention relates to a fuel cell, particularly a method for preparing a θ-plate and a bipolar plate thereof. Bipolar fuel cell [previous technology] Fuel cell _ _ has been widely used in electric power, smart, = reading and low (four) vegetable transport wheel, space, military scorpion in various fields due to its high efficiency response . Fuel cell system - a kind of power generation device that can continuously convert chemical energy into electrical energy continuously. When fuel cell is working, fuel gas (such as preparation #,, wind nitrogen) and combustion improver (such as oxygen chaos) W transport fabric battery The anode and cathode convert chemical energy into electrical energy. 4 Original Reaction The conventional fuel cell unit structure is roughly composed of an anode plate, a cathode plate, and a susceptor-sheet electrolyte membrane, which is called a single cell. However, in actual use, it is necessary to connect a plurality of single cells in series to obtain a larger output voltage, and adjacent fuel cell single systems share the same electrode plate, which are respectively used as two adjacent fuel cell precursors. The anode is too ridiculous, the shirt - the lack of _ _ _ _ this. The material of the plate is mainly made of graphite material, composite carbon material and metal material. In order to cope with the demand for high power density and light weight of the fuel cell in the market, it is bound to be bipolar. Board (four). $, to control the thickness of the graphite 2 or composite carbon plate is extremely thin, which will result in poor airtightness and structural strength of the bipolar plate, or limited by the low hardness and poor ductility of the graphite. The feature 'causes to add or make Xiao Shirong $ broken ^. } 1375347 Metal material is easy to process, suitable for mass production, and has excellent electrical conductivity and thermal conductivity. Therefore, if metal #料 is used, it can be made into a thinner and lighter bipolar plate. However, during the operation of the fuel cell, after the reaction of the fuel or the oxidant, the surface of the metal bipolar plate is oxidized and rotted, resulting in a decrease in the performance of the fuel cell and a shortened service life. If a bipolar plate made of a corrosion-resistant precious metal (such as gold (Au) or platinum (Pt)) is used, or a protective layer of a precious metal material is plated on the surface of the metal bipolar plate, the manufacturing cost is too high. The stainless steel (stainless steel), the inscription material (A1), or the titanium material (Ή) and other anti-corrosion metal materials m double pole (four) f, although the surface of the money plate can form a dense oxide layer composed of oxide, The electrolyte causes the rot of the bipolar filaments', but these oxide layers also cause an increase in the surface contact resistance, so that the ability of the bipolar plates to conduct electrons will be low, and the total output of the domain-derived fuel pool will also decrease. . US patent f 6 money _ fresh grain (four) τ abbreviation _ case) expose a fuel cell bipolar plate, turn, material _ 上 駄 细 细 细 ( ( ( 四 四 四 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( In combination with the substrate, the polymer material is added with at least 9〇% of conductive graphite, so as to isolate the external environment from causing rot and oxidation of the non-thin substrate, and the conductive property is obtained. However, since the 040 case forms a conductive protective film by tilting, and its polymer material (4) volatilizes frequently during high-temperature transfer, the resulting shaped conductive guagen produces small pores in the non-shirt, thus resulting in compactness of the protective film. Poor, and these small pores become the passage of the acidic solution of the fuel cell into the bipolar plate. Because the 〇4〇 must be coated with a multi-layer polymer material on the surface of the stainless steel substrate, and the high temperature cracking process of 1375347 can avoid the above problems, but the processing procedure of the bipolar plate is too complicated and manufactured. The cost is also too expensive. SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a method for preparing a bipolar plate of a fuel cell and a bipolar plate for a fuel cell, thereby improving the bipolar plate of the conventional fuel cell due to the characteristics of the graphite material. Restricted, and the use of poor performance, and the bipolar plates made of metal materials must go through multiple surface treatment procedures, resulting in complex processing procedures and high manufacturing costs. The method for preparing a bipolar plate of a fuel cell according to the present invention, the first step of which is to provide a metal substrate ' and to form a graphite film. Next, a polymer material is supplied onto the surface of the metal substrate, and a conductive powder is added to the polymer material. The stone wing film is placed on the polymer, and the polymer material is cured, and the graphite film is bonded to the metal substrate. The bipolar plate of the invention comprises a metal substrate, an adhesive layer, and a graphite crucible, wherein the adhesive layer is disposed on the surface of the metal substrate, the conductive powder is disposed in the layer, and the graphite film is disposed on the adhesive layer. On the floor. · And ^ 剌 silk completes the stone (four) preparation process, and then the county combines the ink film and the metal substrate, not pre-mixed graphite and high-sorting 将: the stone is molded on the metal substrate, the 本It is different from the injury procedure of the conventional bipolar plate. Further, the preparation method is reversed. Therefore, the preparation method of the present invention can avoid a graphite film, and a large number of defects (d _: layer) are generated inside the molded fin from the bipolar plate to the utility performance 5 1375347 and the service life to reach It is light and thin, can be mass-produced, has good corrosion resistance, and reduces manufacturing costs. The above description of the present invention and the following description of the embodiments are intended to be illustrative of the invention and to provide further explanation of the scope of the invention. [Embodiment] FIG. 1 and FIG. 2 to FIG. 6 are diagrams showing a flow chart and an exploded procedure of an embodiment of the present invention. As shown in "Picture 2" to "3D", and in conjunction with the steps of "Digital Diagram", the method for preparing the bipolar plate of the fuel cell of the present invention is first provided. The metal substrate 210 (step 1 〇〇), this; a metal substrate 21 〇 material can be inscription material (A1), titanium material (Ti), nickel material, copper material ((:: 11), chrome material (( :1>), tin material (Sn) and its alloy, or stainless steel material steei) _, and the metal substrate 210 of this embodiment is made of 316L stainless steel material, and its thickness is 01 mm (_) to 0.2 mm (_) The present invention is not limited to this embodiment. In addition, the fuel cell disclosed in the present invention is a proton exchange membrane cell (I^MFC), but it is not limited thereto. Forming a graphite film 220 (step 110), and the graphite film 22 is pressed and formed by a jig 300. In detail, the forming process of the graphite film 22 is first: for a jig 300 'and then Quantitative graphite material 4〇〇, such as natural graphite or artificial graphite (or expanded graphite) is filled into the heat treatment 300, and then the fixture is 3〇 Applying a pressing force to form a high-purity and dense graphite film 22〇 in a dense pressure. In this embodiment, 6 1375347 graphite film 2 220 _synthetic force is at least 80 kg force per square centimeter (kgW). When the pressing force is lower than 8 G kg/min., the graphite material will not form the silk flat layer as in the present embodiment, and the dense rot effect of the graphite film is relatively deteriorated. The graphite film of this embodiment is moved. For the microstructure, please refer to the scanning electron microscope (s_mg electr〇n nncroscopy, SEM) shown in Figure 7. The thickness of the graphite film is GG1 (face) to 丨 mm (four). The general practitioner can change the thickness and density of the stone galvanized 220 by adding a light amount or a pressure force, which is not in the domain of the embodiment. Alternatively, it can be added to the graphite film 22G. During the lion process, an additional amount of heat is applied to the fixture 3GG to increase the bonding and density of the stone surface 22G. As shown in the "3D", and in conjunction with the "Step 1" step process description, The bipolar (four) preparation method of the invention battery further includes The first path 221 is on one side of the graphite film 220 (step m). It is noted that the flow path 221 on the graphite film 220 can be simultaneously formed in the graphite film 22G during the preparation process of the graphite film 22〇M. The forming step of the flow path 221 is not limited to the embodiment disclosed in the present invention, and the process of forming the flow path 221 is not limited to the embodiment disclosed in the present invention. Please continue to refer to "Attachment 4A". To the "4C", and - take into account the flow chart of the "Figure 1" steps. Then, a polymer material 23 is provided, for example, a thermosetting resin material, a photocurable resin material, or a chemically hard resin material, and a conductive powder 231 is added to the polymer material 230, and the conductive powder 231 is added in a range of 7 Percentage by weight (lwt%) [between 2% by weight (lwt%), and the conductive powder is gold (Au), beginning (Pt), 纪(ρφ, 鈇(Ti), town (Ni), chrome Metal powder such as (Q·) or its alloy, graphite powder, carbon powder, carbon nanotube, carbon fiber, or mixed powder 'The particle size of the conductive powder 231 is controlled at i nm (four) to 2 〇〇 Between meters (nm), however, 'the person skilled in the art can select ', the type of powder with good electrical characteristics, and the suitable powder particle size according to the actual use requirements, and the embodiment disclosed in the present invention is not The polymer material material 230 to which the conductive powder 231 is added is mixed by mechanical means or artificially, so that the conductive powder 231 is uniformly dispersed in the polymer material (10)': then the polymer containing the conductive powder is added Material 23〇 is applied to a surface of the metal substrate 'ho (Step 120) 'The polymer material 23 of the present embodiment can be uniformly applied to the metal substrate by means of knife coating, spin coating, spray coating, slit coating, or roll coating. As shown in "·1st image" and "Fig. 5" and "Fig. 6", the prepared graphite crumb 22 is placed on the polymer material MO (step), and the graphite film 22〇 φ is attached to the polymer material bo by the other side having the flow path 221. Next, the polymer material 230 is cured to form the adhesive layer 232 (step 14A), so that the graphite film 220 is firmly bonded to the metal substrate. 21〇, to become a fuel cell bipolar plate 200 structure. Among them: the thickness of the adhesive layer 232 of this embodiment is controlled between 1 〇 micron (beer) to 600 micron (μιη) 'but not For the sake of limitation, please refer to the polarization curve analysis chart shown in "Figure 8" and "The First Picture". The corrosion solution used in the corrosion test is a sulphuric acid solution with a concentration of 莫·5 mol _ Ϊ 375347 • The test time is 1000 hours. "Fig. 8A" shows the 316L stainless steel not covered with the graphite film of the present invention. The dynamic polarization curve of the substrate was tested for corrosion resistance. The solid line segment was the polarization curve when the 316L stainless steel substrate was not immersed in the sulfuric acid solution. The dotted line segment was the polarization curve after immersing the 316L stainless steel substrate in the sulfuric acid solution for 1000 hours. It can be seen that when the 316L stainless steel substrate not covered with the graphite film is immersed in the sulfuric acid solution for 8 (8) hours, the corrosion current density value is about 1 〇 7 amp / ping without being immersed in the sulfuric acid solution. The square centimeters (Amps/cm2) increased to about 10.6 amps/cm2 (Amps/cm2). It is obvious that the 316L stainless steel substrate not covered with graphite film is in a rotten environment for a long time, and its corrosion resistance is seriously degraded. , which in turn affects the reliability of the fuel cell bipolar plate. "8B" shows the dynamic polarization curve of the corrosion resistance test of the 316B stainless steel substrate coated with the graphite film of the present invention, and the solid line segment is the polarization curve of the 316L stainless steel substrate when not immersed in the sulfuric acid solution, and the dotted line The line segment is a polarization curve after immersing the 316L stainless steel substrate in a sulfuric acid solution for 1000 hours. It can be seen from the figure that when the steel substrate coated with the graphite film is immersed in the sulfuric acid solution, after hours, the rot (four) flow density bribe is not immersed in the mixed solution _ the current value of the contact current is close, There is no obvious change. It is obvious that the 316L non-ferrous steel substrate coated with the graphite film of the present invention is in the rot scale for a long time, and still maintains good anti-corrosion characteristics. Please refer to the curve of the stress_interface contact impedance shown in Figure 9A and Figure 9B. The 'X-axis is the stress value in Newtons per square centimeter (10)^2), and the Y-axis is the resistance. Coefficient (ICR), in milligrams of parent per square centimeter (four) (10). Among them, the '.♦ tiger line segment is uncovered; 5 ink film 316L stainless steel substrate force 1375347 _ interface contact impedance curve; 匾: symbol curve segment is slope coated with graphite film, and the adhesive layer contains conductive powder The stress and interface contact impedance curve of the 316L stainless steel substrate; the curve line segment of the ▲ symbol is the response-interface contact impedance curve of the 316L stainless steel substrate with the graphite film and the conductive layer in the adhesive layer. It can be clearly seen from "Fig. 9A" that the three-dimensional steel substrate coated with a graphite film but not containing conductive powder in the adhesive layer has a higher interface contact resistance value than the other two sets of stainless steel substrates. The addition of conductive powder to the adhesive layer can effectively reduce the interface contact resistance of the bipolar plate. The bipolar plate of the present invention provides the horizontal conductivity of the graphite film, and the conduction of the conductive layer in the transfer layer provides the conductivity of the vertical surface. The bipolar plate of the present invention is provided with relatively good electrical conductivity. In addition, please refer to "Fig. 9B", and compare the stress interface contact impedance curves of the 316 B stainless steel bristles not covered with graphite film and coated with graphite film and containing conductive powder in the adhesive layer. The 31-coated stainless steel substrate coated with graphite film needs to apply a certain degree of stress to reduce the interface contact resistance value, while the interfacial contact of the 316L stainless steel substrate with the graphite film on the slope group and the conductive powder in the lining layer The impedance value is not affected by the stress value and causes a large change. The method for preparing a bipolar plate of a fuel cell according to the present invention is that the graphite film is firstly completed by an adhesive layer formed by hardening the polymer material to bond the graphite film and the metal plate. Therefore, the preparation method of the bipolar plate of the present invention is different from the preparation steps of the conventional bipolar plate, and effectively improves the problem that a conductive protective layer of the bipolar plate for f causes a large number of defects to be formed during dry film formation, and the preparation method of the present invention It can be widely used in the manufacture of bipolar plates for high temperature or low temperature fuel cells. 10 1375347 剌 _ stone _ and (10) double _, called recording metal base burning m Wei Wei recording, such as improving New Zealand (four) conductive efficiency: use poetry, and reliability 'and achieve reduced manufacturing costs, good resistance to fine health And can be mass produced and other effects. Although the embodiments of the present invention are disclosed above, it is not intended to limit the present invention, and those skilled in the art, regardless of the spirit and scope of the present invention, The spirit of the general and the spirit can be done a little

之變更’因此本侧之翻倾翻馳本朗#_之申請專 利範圍所界定者為準。 【圖式簡單說明】 第1圖為本發明之步驟流程圖; 第2圖至第6圖為本發明之分解步驟示意圖; 4': 第7圖為本發明之石墨膜的電子顯微鏡示意圖; 第8A圖為不鏽鋼基板之極化曲線分析圖; 第犯圖為本發明之結合有石墨膜之不鏽鋼基板的·曲線 ®· , 第9Α圖為本發明之應力-界面接觸阻抗之曲線分析圖;以及 第9Β圖為本發明之應力-界面接觸阻抗之曲線分析圖。 【主要元件符號說明】 :. 步驟100 提供一金屬基板 步驟110 成型一石墨膜 步驟111 形成流道於石墨膜的側面上 11 1375347 步驟120 提供一高分子材料至金屬基板的表面上,且高 分子材料内添加有導電粉末 步驟130 將石墨膜設置於南分子材料上 步驟140 硬化高分子材料以成型為一黏著層 200 雙極板 210 金屬基板 .220 石墨膜 221 流道 230 高分子材料 231 導電粉末 232 黏著層 300 治具 400 石墨材料 12The change is therefore subject to the definition of the patent application scope of this side. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing the steps of the present invention; FIGS. 2 to 6 are schematic views showing the decomposition steps of the present invention; 4': FIG. 7 is a schematic view of an electron microscope of the graphite film of the present invention; 8A is a polarization curve analysis diagram of a stainless steel substrate; the first diagram is a curve of a stainless steel substrate combined with a graphite film of the present invention, and FIG. 9 is a curve analysis diagram of the stress-interface contact resistance of the present invention; Figure 9 is a graph showing the stress-interface contact impedance of the present invention. [Description of main component symbols]: Step 100: providing a metal substrate step 110 forming a graphite film step 111 forming a flow path on the side surface of the graphite film 11 1375347 Step 120 providing a polymer material onto the surface of the metal substrate, and the polymer A conductive powder is added to the material. Step 130: Place the graphite film on the south molecular material. Step 140: Harden the polymer material to form an adhesive layer. 200 Bipolar plate 210 Metal substrate. 220 Graphite film 221 Flow path 230 Polymer material 231 Conductive powder 232 Adhesive layer 300 Fixture 400 Graphite material 12

Claims (1)

13753^ 七、申請專利範圍 】袼年项7j?修-¾卷^頁j —種燃料電池之雙極板的製備方法,包括以下步驟·· 提供一金屬基板; 成型一石墨膜; 形成-流道於該石墨膜相對於該金屬基板的另一側面上; 提供-高分子獅雜金屬基板的—表面上,且該高分子 材料内添加有複數個導電粉末;13753^ VII. Patent application scope] The preparation method of the bipolar plate of the fuel cell, including the following steps, providing a metal substrate; forming a graphite film; forming-flow On the other side of the graphite film relative to the metal substrate; on the surface of the polymer lion metal substrate, and a plurality of conductive powders are added to the polymer material; 將該石墨膜設置於該高分子材料上;以及 並使該石墨膜結合 硬化該南分子材料以成型為一黏著層 於該金屬基板上。 2. 如請求項i所述之麵電池之雙極㈣製財法,射該金肩 基板之材質為鋁材料、鈦材料、 材料及其合金、或是不鏽鋼材料:·…、、鉻材料、箱 3. 如句求項!所述之燃料電池之雙極板的製 膜係藉由-料並轉合方式成型。 亥石墨 4. 輸之雙極靖備方法,財該治具 至^為80公斤力/每平方公分。 3料之轉電池之魏㈣_ 屡合方式成型的過財更包括有施加i、中^墨 步驟。 …、里至該治具的 6·如請求項〗所述 13 1375347 7 , 年07月18曰替換頁 7. 如請求項i所述之燃料電池之雙極板的製 膜的厚度範圍為0.01宅米至1亳米之間。 8. 如請求項1所述之燃魏池之雙極板賴備方法,其中該些導 電粉末為金屬粉末、石墨粉末、碳粉末、奈米碳管、碳纖維、 或是其混合粉末。 9. 如請求項8所述之燃料電池之雙極板的製備方法,其中該金屬 粉末為金、鉑、把、鈦、錄、鉻或其合金。 瓜如請求们所述之燃料電池之雙極板的製備方法,其中該些導 电叔末之尺寸她圍為1奈米至2〇〇奈米之間。 11. 如請求項丨所述之㈣電池之雙極板的製備方法,其中該些導 電粉末的添加細為1個重量百分比至2〇個重量百分比之間。 12. 如請求項〗所述之燃料電池之雙極板的製備方法,其中該高^ :材料係關刀塗佈、旋轉塗佈、噴射塗佈、狹縫塗佈、= 壓塗佈方式塗覆於該金屬基板上。 13. 如請求項〗所述之燃料電池之雙極板的製備方法,其中該高分 子材料之材質為熱硬化樹脂材料、光硬化樹脂材料、或是化二 硬化樹脂材料。 千 R如請求項1所皱之燃料電池之雙極板的賴方法,其中該黏著 層之厚度範圍為10微米至600微米之間。 B,-種燃料電池之雙極板,包括有·· 一金屬基板; 一黏著層’設置於該金屬基板的—表面上,頭黏著層内 14 Ml年07月18曰替換頁 具有複數個導電粉末;以及 一石墨膜,設置於該黏著層上。 ^項15所奴簡電池之雙極板,射該金屬基板之材 2材料、_、錄材料、鋼材料、_、錫材料及1 合金、或是不鏽鋼材料。 八 17.如2項15所述之燃料電池之雙極板,射該石墨膜係藉由 一治具並以壓合方式成型。 17蘭之_魏之雙極板,_料之壓合力 里為至少80公斤力/每平方公分。 19.如請求項15所述之燃 A壬妙 之雙_’其中該石墨膜之材質 為天然石墨或是人造石墨。 可貝 讥如請求項15所述之燃料電池之 範圍為0.01毫米至i毫米之間。 -中該石墨膜的厚度 21. 如請求項15所述之燃 金屬於古 ,又極板,其中該些導電粉末為 i屬柘末、石墨粉末、碳 ^ 合粉末。 7末、米碳管、碳纖維、或是其混 22. 如請求項21所述之_ λ ,之又極板,其中該金屬粉末為全、 翻、纪、鈦、鍊、鉻或其合金。 木〜 23·如請求項15所述之綠料 j, €池之又極板,其中該些導電粉末之 尺寸耗圍為1奈米至枷奈米之間。 末 24.如請求们5所述之 添加範圍為i個重量ft 中該些導電粉末的 刀比至20個重量百分比之間。 15 1375347 = 之燃料電池之雙極板, 刀塗佈、旋轉塗佈、噴射 黏者層係_ 置於該金屬基板上。师狹縫塗佈、或滚屋塗佈方式設 26. 如.月求項15所述之燃料電池之雙極板, 為熱硬蝴旨倾、細咖 ,、+雜者層之材質 27. 如請求項15所述之燃料電 板=學硬化樹脂材料。 範圍為K)微米至_微米之間雙板,其中該黏著層之厚度 犹如請求項15所述之燃料電池之雙極板, 該金屬基板的另一側面更具有一故、,/、甲茲石墨膜相對於The graphite film is disposed on the polymer material; and the graphite film is bonded and hardened to form an adhesive layer on the metal substrate. 2. According to the bipolar (four) method of making a battery according to claim i, the material of the gold shoulder substrate is aluminum material, titanium material, material and alloy thereof, or stainless steel material: ..., chrome material, Box 3. As an example! The film of the bipolar plate of the fuel cell is formed by a material and a transfer method. Hai graphite 4. The bipolar method of the loss, the tool is to ^ 80 kg / per square centimeter. 3 material transfer battery Wei (four) _ repeated method of forming the rich money also includes the application of i, medium ^ ink steps. ..., to the jig of the jig, as described in the claim, 13 1375347 7 , July 18, 曰 Replacement page 7. The thickness of the film of the bipolar plate of the fuel cell as described in claim i is 0.01 House rice to 1 meter. 8. The method according to claim 1, wherein the conductive powder is a metal powder, a graphite powder, a carbon powder, a carbon nanotube, a carbon fiber, or a mixed powder thereof. 9. The method of preparing a bipolar plate for a fuel cell according to claim 8, wherein the metal powder is gold, platinum, palladium, titanium, chrome, chromium or an alloy thereof. The method for preparing a bipolar plate of a fuel cell as claimed in the above, wherein the size of the electrically conductive uncle is between 1 nm and 2 nm. 11. The method according to claim 4, wherein the addition of the conductive powder is between 1% by weight and 2% by weight. 12. The method for preparing a bipolar plate of a fuel cell according to claim 1, wherein the material is a knife coating, a spin coating, a spray coating, a slit coating, a press coating method. Covered on the metal substrate. 13. The method of preparing a bipolar plate for a fuel cell according to claim 1, wherein the material of the high molecular material is a thermosetting resin material, a photocurable resin material, or a bismuth hardening resin material. A method of applying a bipolar plate of a fuel cell as claimed in claim 1, wherein the thickness of the adhesive layer ranges from 10 micrometers to 600 micrometers. B, - a bipolar plate of a fuel cell, comprising a metal substrate; an adhesive layer 'on the surface of the metal substrate, the first adhesive layer in the head adhesion layer 14 Ml July 18 曰 replacement page has a plurality of conductive a powder; and a graphite film disposed on the adhesive layer. ^ Item 15 The battery of the bipolar plate, the material of the metal substrate 2 materials, _, recorded materials, steel materials, _, tin materials and 1 alloy, or stainless steel. 8. The bipolar plate of a fuel cell according to item 15, wherein the graphite film is formed by a jig and pressed. 17 Lanzhi_Wei's bipolar plate, _ material pressure is at least 80 kg force / square centimeter. 19. The fuel of the graphite film according to claim 15 wherein the material of the graphite film is natural graphite or artificial graphite. The fuel cell of claim 15 may range from 0.01 mm to 1 mm. - The thickness of the graphite film. 21. The metal according to claim 15 is a conventional one, wherein the conductive powder is a genus, a graphite powder, a carbon powder. 7, carbon nanotubes, carbon fibers, or a mixture thereof 22. The _λ, as described in claim 21, is a plate in which the metal powder is full, turned, quaternary, titanium, chain, chromium or alloys thereof. Wood ~ 23 · The green material j of the claim 15, the further plate of the pool, wherein the conductive powder has a size of between 1 nm and 枷 nanometer. 24. The addition range is as described in claim 5 for a knife ratio of the conductive powder of i weight ft to between 20 weight percent. 15 1375347 = The bipolar plate of the fuel cell, knife coating, spin coating, spray coating layer _ placed on the metal substrate. The slit coating or the rolling house coating method is provided. 26. The bipolar plate of the fuel cell described in Item 15 of the month is a material for the heat hardening, the fine coffee, and the material of the miscellaneous layer. The fuel panel as claimed in claim 15 is a hardened resin material. The range is K) micron to _micron between the two plates, wherein the thickness of the adhesive layer is as in the bipolar plate of the fuel cell described in claim 15, the other side of the metal substrate is more than one, /, Graphite film relative to
TW098139650A 2009-11-20 2009-11-20 Manufacture method of bi-polar plates of fuel cell and bi-polar plates thereof TWI375347B (en)

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